Anticounterfeiting Feature of a Writable and Self-Erasable Ni(II)-Metallogel Pad via Fluorescent “Turn-On” Detection of Cyanide

A Schiff
base 5-(2-hydroxy-3-methoxybenzylidieneamino)-1-H-imidazole-4-carboxamide (HL) comprising multibinding
sites has been synthesized with the aim of fabricating a supramolecular
gel. The gelator HL was characterized by FT-IR, 1H & 13C NMR, and ESI-MS techniques and also
formed a [Ni(L)2] complex. The gelation property of HL was investigated with various metal ions, wherein Ni(II)
selectively forms a mechanically and thermally stable supramolecular
metallogel (MG) in the presence of a triethylamine base
in DMF-MeOH media. Characterization of MG was accomplished
with different spectro-analytical techniques such as FT-IR, ESI-MS,
powder-XRD, SEM, rheological investigations, UV/vis, and fluorescence.
The gelator HL displays moderate emission upon addition
of Ni2+ and gives “turn-off” fluorescence
output by forming the complex [Ni(L)2] (MG) due to the chelation-enhanced quenching of fluorescence (CHEQ).
Job plot and ESI-MS data suggested a 2:1 stoichiometry between HL and Ni(II) in MG. Further, MG exhibited highly selective and ultrasensitive “turn-on” fluorescence signaling with CN– in the
background presence of several cations and anions. The limit of detection
(LoD) of MG was determined to be 6.9 × 10–9 M for CN– using the fluorescence technique. Notably, MG behaves as a fluorescent writable pad material explicitly
with CN– under 365 nm UV light but not under ordinary
light and the fluorescent text is self-erased after 15 min. Hence, MG can be used as a metallogel pad in the presence of CN– to communicate secret messages. Overall, the present
work explores the fabrication of a thermo- and mechanostable Ni(II)-metallogel
(MG), which selectively and ultrasensitively detects
CN– both in the solution phase and in the gel form,
wherein MG behaves as a writable and self-erasable pad
with anticounterfeiting features for practical applications.